Low-haze ionomers of copolymers of alpha-olefins, carboxylic acid esters, and optional comonomers, and processes for making and acidifying these ionomers

ABSTRACT

Ionomer compositions which have improved optical properties are disclosed. These compositions comprise ionomers which can be represented as the polymerization product of alpha-olefins having from two to eight carbon atoms, esters of alpha, beta-ethylenically-unsaturated carboxylic acids, metal salts of acrylic and methacrylic acid, and optional alpha, beta-ethylenically-unsaturated comonomers which impart some desired polymer property or properties, such as acidity and/or solvent resistivity. Also disclosed are methods of making these ionomer compositions in a reactive extruder and treating the compositions with acid to impart acidity to the compositions or to only the surface of the compositions.

This application is a continuation of U.S. Ser. No. 08/379,411, filedJan. 27, 1995, which is a continuation-in-part application of U.S. Ser.No. 08/330,290, filed Oct. 27, 1994, which is a continuation-in-partapplication of U.S. Ser. No. 08/144,173, filed Oct. 27, 1993 nowabandoned.

BACKGROUND

This invention provides new polymeric ionomer compositions which havelow haze. Low haze makes the compositions especially suited for use inclear packaging films, in addition to the other applications in whichionomers are utilized. This invention also provides a method for makingthese new polymeric compositions and for modifying the acidity of thecompositions.

The compositions comprise ionomers which can be represented as thepolymerization product of alpha-olefins having from two to eight carbonatoms, esters of alpha, beta-ethylenically-unsaturated carboxylic acids,metal salts of acrylic and methacrylic acid, and optional alpha,beta-ethylenically-unsaturated comonomers which impart some desiredpolymer property or properties, such as acidity and/or solventresistivity. These ionomer compositions can easily be formed into films.

Ionomers which can be formed into films and methods of making ionomersare known in the art. Although these previously-known ionomers havesimilar chemical constituents to the ionomer compositions of thisinvention, the known ionomers have significantly different propertiesfrom the compositions of this invention. In addition, the knownprocesses for making ionomers are also quite different from the methodof making compositions of the present invention.

Japanese patent number Sho 49-31556 to Iwami et al., dated Aug. 22,1974, discloses a process for making ionomers which comprisessaponifying copolymers of ethylene and alpha,beta-ethylenically-unsaturated carboxylate esters with a basic metalcompound in aliphatic alcohol or in an organic solvent containing analiphatic alcohol. The copolymer is homogeneously or heterogeneouslydispersed in the alcohol solution. The saponified product can be furtheracidified to provide a composition having acid groups. Although theionomers which have acid functionality are said to have low haze, nohaze values are provided for ionomers which have no acid functionality.

Japanese patent number Sho 53-134591 to Harada et al., dated Nov. 24,1978, discloses a film made by the process of Sho 49-31556 which is saidto be useful for stretch-wrap applications. Their ionomer comprises acopolymer having 90-98 mole percent ethylene, 9.7 to 2.0 mole percent ofan alkyl ester of an unsaturated carboxylic acid, 0 to 2.5 mole percentof unsaturated carboxylic acid, and 0.3 to 2.5 mole percent of a metalsalt of an unsaturated carboxylic acid. It is stated that their film hasvery good mechanical, thermal, and optical properties, but the film islimited to having less than 9.7 mole percent ester to prevent blockingoccurs between film layers. In addition, the copolymer is limited to amaximum of 2.5 mole percent metal salt of an unsaturated carboxylic acidabove which the viscosity of the copolymer is too high to allowprocessing of the copolymer. All copolymers in the films of the examplescontain an unsaturated carboxylic acid component, which, the patentstates, is used to adjust the modulus of elasticity and transparency ofthe film.

U.S. Pat. No. 5,218,057, issued to V. Kurkov and L. Theard on Jun. 8,1993 and which is incorporated by reference in its entirety, teaches aprocess for saponifying an ethylene alkyl acrylate copolymer whichcomprises adding an aqueous solution of an inorganic alkali metal baseto a molten ethylene-alkyl acrylate copolymer and mixing the alkalimetal base and copolymer at a temperature sufficient for saponificationto take place and at which the ethylene-alkyl acrylate copolymer remainsin a molten or fluid state. Copolymers made by this process have lowertensile strength, lower gloss, and much higher haze than the copolymersof the present invention.

U.S. Pat. No. 4,638,034 to McClain, dated Jan. 20, 1987 and which isincorporated by reference in its entirety, claims a process forpreparing an ethylene-acrylic acid copolymer salt which comprisessaponifying an ethylene-alkyl acrylate copolymer in the molten state, inthe absence of solvent or water other than by-product alkanol, withalkali metal hydroxide or alkaline earth metal hydroxide undernon-static mixing conditions so as to thereby form alkanol and an alkalimetal or alkaline earth metal salt of ethylene-acrylic acid copolymer,and separately recovering the alkanol and the salt.

U.S. Pat. No. 3,970,626 to Hurst et al., dated Jul. 20, 1976, disclosesa copolymer of ethylene, alkyl acrylate or methacrylate, and an alkalimetal salt of acrylic or methacrylic acid. Although this patent ismainly concerned with forming copolymers which form stable aqueousemulsions, the patent states that the copolymer can be extruded intofilms of good flexibility. Copolymers in the examples are formed using abatch autoclave. It is stated that about a one-fold excess of sodiumhydroxide over what is theoretically required is used to convert theester groups.

U.S. Pat. No. 4,042,766 to Tatsukami et al., dated Aug. 16, 1977 andwhich is incorporated by reference in its entirety, provides a methodfor preparing ionically cross-linked copolymers comprising melt-blendinga copolymer comprising 1) ethylene and 2) at least one alkyl acrylate ormethacrylate where the alkyl is selected from the group consisting ofisopropyl or tert-butyl, with 3) at least one metal compound selectedfrom the group consisting of acetates, formates, and oxides of zinc,magnesium, calcium, and sodium, and maintaining the molten blend at atemperature of about 200° to 320° C. The patent states that high mixingefficiency is desirable in the reaction equipment to assure uniformdispersion of the metal compound into the ester copolymer and to assurequick evaporation of the low molecular-weight byproducts, such as bymelt-blending the components. Per the patent, adequate mixing wasprovided by a 20 mm-diameter single-screw extruder having a retentiontime of about one minute, as illustrated in Example 1 of that patent.

U.S. Pat. No. 3,789,035 to Iwami et al., dated Jan. 29, 1974 and whichis incorporated by reference in its entirety, discusses three methodsfor acidifying an ionomer of a copolymer of ethylene and an ester of analpha, beta-ethylenically-unsaturated carboxylic acid. The ionomer ismade by saponifying a copolymer of ethylene and an ester of an alpha,beta-ethylenically-unsaturated carboxylic acid with a basic metalcompound in a solvent containing an alcohol. The patent states that thealcohol is used to promote the reaction of the basic metal compound withthe copolymer. The ionomer is then acidified by either 1) adding acidand replacing some of the basic metal with hydrogen; 2) melt-blending apolymer having acid groups with an ionomer; or 3) exchanging anon-alkali metal ion with the alkali metal ion on the ionomer which hasbeen dispersed in a solvent.

U.S. Pat. No. 3,264,272 to Rees, dated Aug. 2, 1966, claims acomposition comprising a random copolymer of an alpha-olefin having fromtwo to ten carbon atoms, an alpha, beta-ethylenically-unsaturatedcarboxylic acid having from three to eight carbon atoms in which 10 to90 percent of the acid is neutralized with metal ions, and an optionalthird mono-ethylenically unsaturated comonomer such as methylmethacrylate or ethyl acrylate. This copolymer is acidic due to thecarboxylic acid groups present in the copolymer. U.S. Pat. No. 3,404,134discloses the process for making these compositions, which comprisesreacting an ethylene acrylic acid copolymer with a metal compound at apressure between 100 and 10,000 psi and a temperature above themelt-point of the copolymer.

U.S. Pat. No. 5,189,113 to Muehlenbernd et al., dated Feb. 23, 1993,discloses a process for making ionically cross-linked copolymers ofethylene and alpha, beta-ethylenically-unsaturated carboxylic acids oralpha, beta-ethylenically-unsaturated comonomers donating carboxylgroups, such as anhydrides. This process requires reacting the copolymerwith a solid metal compound in a mixing zone of a twin-screw extruderand subsequently pumping in water. The advantages for this process aresaid to be that no discoloration of the ionomer occurs because nocorrosion of the twin-screw extruder occurs, and no specks of unreactedsolid metal compound are found in the ionomer film.

U.S. Pat. No. 5,003,001 to Hasenbein et al., dated Mar. 26, 1991, claimsa process for making ionically cross-linked copolymers of ethylene andalpha, beta-ethylenically-unsaturated carboxylic acids or alpha,beta-ethylenically-unsaturated comonomers donating carboxyl groups, suchas anhydrides. This process reacts the copolymer with an aqueous metalsalt solution in a first reaction zone at a temperature from 140° to180° C. to form ionomer and completely devolatilizes the ionomer in asecond, three-stage devolatilization zone at a temperature from 200° to270° C. This process is said to provide odor-free ionomer film which isfree of specks.

Although there has been much research in the area of ionomers, what hasbeen lacking in the prior art is optically clear ionomers comprisingcopolymers of alpha olefins having two to eight carbon atoms, esters ofalpha, beta-ethylenically-unsaturated carboxylic acids, and metal saltsof alpha, beta-ethylenically-unsaturated carboxylic acids as well asmethods of making those ionomers. This invention provides suchcompositions and methods.

SUMMARY OF THE INVENTION

In one embodiment, the invention comprises a copolymer of alpha-olefinshaving from two to eight carbon atoms, esters of alpha,beta-ethylenically-unsaturated carboxylic acids having from four totwenty-two carbon atoms, and metal salts of acrylic or methacrylic acid,wherein this copolymer has a haze of no more than ten percent asmeasured by ASTM method D 1003.

In one preferred embodiment, the invention comprises a copolymer ofethylene, methyl acrylate, and sodium salt of acrylic acid, wherein thehaze of the copolymer is no more than five percent.

In another embodiment, the invention comprises a method of making anionomer composition. This method comprises contacting a Group IAmetal-containing solution with a molten or fluid copolymer comprisingalpha-olefins having from two to eight carbon atoms and esters of alpha,beta-ethylenically-unsaturated carboxylic acids having from four totwenty two carbon atoms and having a melt index between about 100 andabout 2000 g/10 min., as measured by ASTM method D 1239 at 190° C. usinga 2.16 kg weight; and intensively mixing the copolymer and Group IAmetal-containing solution at a temperature and to an extent whichprovides an ionomer composition having no more than ten percent haze.

In another embodiment, the invention comprises a method of reducing thewater solubility of an ionomer composition formed into a shape such asstrands, pellets, or film, which method comprises contacting a surfaceof the shape with an acid.

Among other factors, the present invention is based on our finding thatfilms of the composition as described herein have very low haze,particularly when the films are made after saponifying a copolymer asdescribed above under conditions which include intensive mixing, agreater extent of saponification, and higher reaction temperatures. Filmhaze is no more than ten percent, and many films have a haze of no morethan five or even two percent. Furthermore, in a preferred embodiment,the composition has improved properties such as improved tensilestrength, hot tack strength, and/or heat seal strength over ionomers ofsimilar composition.

In addition to the properties discussed above, many of the compositionsof this invention have no acidity, regardless of the extent ofsaponification. These advantages and others are further described below.

DESCRIPTION OF THE FIGURES

FIG. 1 is a scanning electron micrograph of a freeze-fracturedcross-section of 3-mil thick film made from an ionomer composition ofthis invention, taken at a magnification factor of 8,000.

FIG. 2 is a scanning electron micrograph of a freeze-fracturedcross-section of 3-mil thick film of ionomer of Comparative Example G.FIG. 2 illustrates that spherical and oblong ionic clusters or regionsare present in the ionomer. This micrograph was also produced at amagnification factor of 8,000.

A JEOL JSM-820 scanning electron microscope was used to generate themicrographs. The micrographs of FIGS. 1 and 2 show the fracture surfaceof films which were made by the blown film process of the examples.

FIG. 3 shows the hot-tack of ionomer of this invention from Example 20as a function of temperature. The ordinate is temperature in °C., andthe abscissa is hot-tack, measured in Newtons/inch. Line 1 is 35%hydrolyzed ionomer, line 2 is 42% hydrolyzed ionomer, and line 3 is 50%hydrolyzed ionomer.

FIG. 4 shows the heat seal strength of the ionomer/polyethylene film ofExample 22 as a function of temperature. The ordinate is temperature in°F. and the abscissa is the heat seal strength in lb/inch.

DETAILED DESCRIPTION OF THE INVENTION

A. Compositions

Compositions of this invention can be represented as thecopolymerization product which contains the following comonomers:

(a) alpha-olefins having from 2 to 8 carbon atoms,

(b) esters of alpha,beta-ethylenically-unsaturated carboxylic acids,

(c) metal salts of acrylic or methacrylic acid, and

(d) optionally, other alpha, beta-ethylenically-unsaturated comonomerswhich impart desirable polymer properties.

These compositions have no more than ten percent haze, preferably nomore than seven percent haze, and more preferably, no more than fivepercent haze. The most preferred compositions have no more than twopercent haze. Additionally, these compositions have very good hot tackstrength, heat seal strength, and mechanical properties such as tensilestrength. Acid functionality can also be introduced into these ionomers.

Examples of compositions of this invention include ethylene-methylacrylate-sodium acrylate ionomer, ethylene-methyl methacrylate-sodiummethacrylate ionomer, ethylene-ethyl acrylate-sodium acrylate ionomer,ethylene-propylene-methyl acrylate-sodium acrylate ionomer,ethylene-propylene-methyl methacrylate-sodium methacrylate ionomer,ethylene-methyl acrylate-lithium acrylate ionomer, ethylene-methylacrylate-potassium acrylate ionomer, ethylene-methyl acrylate-cobalt(II)or (III) acrylate ionomer, ethylene-methyl acrylate-zinc acrylateionomer, ethylene-methyl acrylate-titanium(II), (III), or (IV) acrylateionomer, ethylene-methyl acrylate-magnesium acrylate ionomer,ethylene-methyl acrylate-iron(II) or (III) acrylate ionomer,ethylene-methyl acrylate-nickel(II) or (III) acrylate ionomer,ethylene-methyl acrylate-copper(I) or (II) acrylate ionomer,ethylene-methyl acrylate-acrylic acid-sodium acrylate ionomer,ethylene-methyl methacrylate-methacrylic acid-sodium methacrylateionomer, ethylene-methyl acrylate-sodium acrylate ionomer grafted withmaleic anhydride, ethylene-methyl acrylate-maleic anhydride-sodiumacrylate ionomer, and acrylic acid-grafted-(ethylene-methylacrylate-sodium acrylate) ionomer.

Monomer (a) comprises alpha-olefins having from 2 to 8 carbon atoms.Preferably, monomer (a) comprises alpha-olefins having from 2 to 3carbon atoms, and more preferably, monomer (a) consists essentially ofethylene.

Monomer (b) comprises esters of alpha, beta-ethylenically-unsaturatedcarboxylic acids having from 4 to 22 carbon atoms. Preferably, monomer(b) has from 4 to 13 carbon atoms, and more preferably has from 4 to 8carbon atoms. Examples of monomer (b) include methyl acrylate, methylmethacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, andbutyl methacrylate. Methyl acrylate is the preferred monomer (b).

Monomer (c) is a metal salt of acrylic or methacrylic acid. The metalion is selected from Group IA, Group IIA, and transition metal ions. Themetal ions may also be aluminum, gallium, germanium, and tin. Otherexamples include lithium, sodium, potassium, rubidium, cesium, calcium,magnesium, zinc, titanium, iron, cobalt, nickel, and copper. Preferably,the metal ion is a Group IA or Group IIA metal ion, and more preferably,the metal ion is a Group IA metal ion. Most preferred is sodium. Monomer(c) is about 25 to 99 mole percent of the total amount of (b) and (c)present in a composition. Preferably, monomer (c) is about 35 to 80, andmore preferably, is about 40 to 60, mole percent of the total amount of(b) and (c) present in a composition.

Typically, a composition of this invention contains from about 1 to 20mole percent of monomers (b) and (c) in total. Preferably, a compositioncontains about 3.5 to 12.5 mole percent, and more preferably, about 5.5to 10 mole percent of monomers (b) and (c). Most preferred is acomposition containing about 7.5 to 10 mole percent of monomers (b) and(c).

Monomer (d) is an alpha, beta-ethylenically-unsaturated comonomer whichimparts certain desired polymer properties. The amount and type ofmonomer (d) are determined by the particular properties that are desiredin the final composition. For example, monomer (d) may be acrylic ormethacrylic acid which is present in an amount that provides the desiredacid functionality to the composition. Other examples of monomer (d)include maleic anhydride and maleic acids to impart acidity,acrylonitrile to impart solvent resistance, and styrene to increase therigidity of the composition. Typically, the compositions contain 0 to 10mole percent of monomer (d). Preferred compositions contain 0 to 5 molepercent of monomer (d).

Monomer (d) can also be added by grafting a group such as acrylic acidor maleic anhydride to a composition of the present invention or to oneof the composition's precursors. As a result, compositions can comprisegrafted (ethylene, (meth)acrylate, metal salt of (meth)acrylic acid)copolymers. Maleic anhydride-grafted (ethylene, methyl acrylate, sodiumacrylate) copolymer is one such composition.

The ionomer compositions of this invention have a number of surprisingfeatures which distinguish them from other ionomers having similarchemical constituents. The ionomers of this invention are quite clear.Haze is typically no more than 5 percent. Also, in one preferredembodiment, the 60° gloss is typically at least 100, and in manyinstances, is at least 120. In another preferred embodiment, tensilestrength of the composition is improved over ionomers of similarcomposition by 100-300 percent. Hot-tack strength and heat seal strengthcan also be improved over ionomers of similar composition. Combinationsof these improved features are present in some preferred compositions ofthis invention.

For example, the haze, gloss, and tensile strength of ionomer of thisinvention are substantially different from the haze, gloss, and tensilestrength of ionomer made by the process of U.S. Pat. No. 5,218,057.Ethylene-methyl acrylate copolymer having about 20 weight percent (about7.5 mole percent) methyl acrylate and having about 65% of the methylacrylate saponified with aqueous sodium hydroxide according to theprocess of U.S. Pat. No. 5,218,057 had a haze of 15% and 60° gloss of66. Tensile strength of an ethylene-methyl acrylate copolymer having 20weight percent methyl acrylate which had about 60% of the methylacrylate groups saponified with aqueous sodium hydroxide according tothe process of U.S. Pat. No. 5,218,057 was 1582 psi in the machinedirection. A composition of the present invention made by saponifying anethylene-methyl acrylate copolymer having about 20 weight percent methylacrylate with aqueous sodium hydroxide to convert about 65% of themethyl acrylate groups had a haze of 2%, gloss of 133, and tensilestrength in the machine direction of 4010 psi.

The ionomers of this invention also can be formed into very thin film.When blowing film, the blow-up ratio can be as high as 2:1 to about2.5:1. Typically, a film of ionomer of this invention can have athickness of less than about 1 mil. Film having a thickness of about 0.5mil has been made, and film having a thickness of about 0.2-0.3 mil canbe made on conventional processing equipment.

The morphology of prior art ionomers can also differ substantially fromthe morphology of ionomers of this invention. Prior-art ionomers cancontain highly localized and large clusters of ionic material dispersedthroughout the ionomer. Scanning-electron micrographs have shown thatthese clusters can range in size from about 0.05 micron to greater than1 micron in size.

FIG. 2 is a scanning-electron micrograph for the ionomer of ComparativeExample G. This ionomer consists essentially of ethylene, 5.7 molepercent methyl acrylate, and 1.8 mole percent of the sodium salt ofacrylic acid. The spherical or oblong ionic clusters evident in thismicrograph range in size from about 0.1 micron to about 0.5 micron. Theclusters were determined to be ionic by energy-dispersive X-rayspectroscopy, which showed a higher sodium content within the clusterswhen compared to the surrounding continuous phase.

FIG. 1 is a scanning-electron micrograph for ionomer composition of thisinvention, which consists essentially of ethylene, 3.7 mole percentmethyl acrylate, and 3.7 mole percent of the sodium salt of acrylicacid. This ionomer composition is substantially free of ionic clustersof the size seen in FIG. 2, since essentially no ionic clusters areobserved in this micrograph. An ionomer composition which issubstantially free of ionic clusters contains essentially no ionicclusters about 0.05 micron in size or larger when a freeze-fracturedcross-section of 3-mil thick blown film which is made by the method ofExample 1 is viewed with a scanning electron microscope at amagnification factor of 8,000. An ionomer composition which issubstantially free of ionic clusters will also have a haze of no morethan ten percent. The ionomer composition of FIG. 1 corresponds to thecomposition of Example 12, which had a haze of 3%. The large flecks ofdebris in FIG. 1 are believed to be foreign matter. The flecks are notregions having high sodium content.

Additives well-known in the art may be included in the ionomer, such asanti-block and slip additives and antioxidants. Preferably, thecomposition of this invention also contains a polymeric acid having amolecular weight of less than about 10,000, such as ethylene acrylicacid. Ionomer compositions containing these low molecular weight acidsare disclosed in copending U.S. Ser. No. 08/188,848, filed Jan. 31,1994, which is incorporated by reference in its entirety herein.

B. Method for making the compositions

One method for making compositions of this invention comprisessaponifying a copolymer having ester groups with a Group IAmetal-containing solution. To obtain the clear ionomer compositions ofthis invention, it is important to provide intensive mixing of thecopolymer and the Group IA metal-containing solution and to have atemperature and/or extent of saponification high enough that asubstantially uniform saponification of the copolymer occurs. Thismethod minimizes the production of localized ionomer regions or domains,which appear as the spherical and oblong ionic clusters of FIG. 2. Thismethod also permits a greater extent of saponification of the copolymerwithout obtaining a saponified product that has so high of a viscositythat it cannot be formed into a film on conventional equipment.

Intensive mixing of the reaction components results from selection ofreactants with the appropriate physical and chemical characteristics andselection of the proper processing conditions. Particular processingconditions are discussed below for a reactive extruder. However, thegeneral principles disclosed therein apply to processes which areequivalent to saponifying a copolymer with a Group IA metal-containingsolution in a reactive extruder.

(1) Reactants

(a) Copolymer to be saponified

The copolymers which are saponified comprise copolymers of ethylene,esters of alpha, beta-ethylenically-unsaturated carboxylic acids, andoptional alpha, beta-ethylenically-unsaturated comonomers which impartdesirable polymer properties. Typically, these copolymers contain fromabout 1 to 20 mole percent of esters of alpha,beta-ethylenically-unsaturated carboxylic acids in total. Preferably,the copolymers contain about 2 to 20 mole percent, more preferably 3.5to 12.5 mole percent, and even more preferably, about 5.5 to 12.5 molepercent of esters of alpha, beta-ethylenically-unsaturated carboxylicacids in total. Most preferred are those copolymers containing about 6.5to 10 mole percent of esters of alpha, beta-ethylenically-unsaturatedcarboxylic acids. The preferred esters are alkyl acrylates. Preferably,the alkyl group contains from one to eight carbon atoms, and morepreferably contains from one to four carbon atoms. Methyl is a preferredalkyl group.

Examples of the copolymers which are saponified include ethylene-methylacrylate copolymer, ethylene-methyl methacrylate copolymer,ethylene-ethyl acrylate copolymer, ethylene-propylene-methyl acrylatecopolymer, ethylene-propylene-methyl methacrylate copolymer,ethylene-methyl acrylate-acrylic acid copolymer, ethylene-methylmethacrylate-methacrylic acid copolymer, maleicanhydride-grafted-ethylene-methyl acrylate copolymer, ethylene-methylacrylate-maleic anhydride copolymer, acrylicacid-grafted-ethylene-methyl acrylate copolymer, and ethylene-methylacrylate-butyl acrylate copolymer. Preferably, the copolymers areethylene-methyl acrylate copolymer, ethylene-methyl methacrylatecopolymer, ethylene-ethyl acrylate copolymer, maleicanhydride-grafted-ethylene-methyl acrylate copolymer, andethylene-methyl acrylate-butyl acrylate copolymer. Most preferred isethylene-methyl acrylate copolymer.

The melt index of copolymers to be saponified should be between about100 and 2000, preferably between about 200 and 800, and more preferablybetween about 300 and 600 grams/10 minutes. Copolymers having highermelt-index values are preferred when it is desired to have a saponifiedcomposition with a higher melt index. One process for making thesecopolymers comprises polymerizing ethylene, alkyl acrylate and/or alkylmethacrylate, and the optional comonomer in autoclaves usingfree-radical initiation catalysts. This process is described in U.S.Pat. No. 3,350,372, which is incorporated by reference in its entirety.The copolymers of the examples were made by this method, unlessspecified otherwise. In one preferred embodiment, the ethylene-alkylacrylate copolymer is made by the process described in copending U.S.Ser. No. 07/947,870, filed Sep. 21, 1992 (published as WO 93/06137),which is incorporated by reference in its entirety herein. Copolymermade by this process has a substantially higher melt-point temperaturethan the copolymer made by the process of U.S. Pat. No. 3,350,372. Theionomer of this invention has high melt point temperature and highclarity when made with this copolymer. Another process for producingcopolymers useful in making the ionomer compositions of this inventioncomprises free-radical polymerization of ethylene and alkyl acrylateand/or alkyl methacrylate as described above, followed by reactiveextrusion with a compound such as acrylic acid or maleic anhydride.Alternatively, grafting may be performed after saponification. Aparticularly preferred copolymer is ethylene-methyl acrylate copolymerhaving between about 5.5 and 12.5 mole percent methyl acrylate andhaving a melt index of about 400 g/10 min., available from ChevronChemical Company as EMAC® copolymer.

(b) Group IA metal-containing solution

The Group IA metal-containing solution comprises a Group IA metal in asolvent, which solvent does not prevent saponification of an ester bythe Group IA metal. The solvent is preferably one which evaporatesreadily under devolatilization conditions typically encountered inreactive extruders. Solvents can be organic or inorganic, and commonsolvents include water, alcohols, and polyethylene glycols, with waterbeing preferred.

The Group IA metal-containing solution has at least one Group IA metalpresent. Preferably, the solution comprises an aqueous solution of aGroup IA metal oxide and/or hydroxide, such as oxides and hydroxides oflithium, sodium, potassium, rubidium, and/or cesium. Preferably, theGroup IA metal-containing solution comprises aqueous sodium hydroxide oraqueous potassium hydroxide.

It is important that the overall concentration of metals in the Group IAmetal-containing solution is low enough that the solution is capable ofbeing mixed uniformly and intensively with melted copolymer in areaction section of a reactive extruder. However, it is preferred tohave only that amount of solvent present that is necessary to providethis capability. Normally, a sufficient quantity of solvent is presentwhen the Group IA metal-containing solution contains little or no excesssolvent beyond that required to solubilize essentially all of the GroupIA metal and other metals present. Thus, for example, 50% aqueouscaustic solution is preferred over 35% aqueous caustic solution.

The Group IA metal-containing solution may optionally contain othermetal oxides, hydroxides, and/or salts which supply cations for monomer(c). The metal ions can be alkaline earth or transition-element metals.Specific examples of these metals include calcium, magnesium, zinc,titanium, cobalt, nickel, and copper. Typical anions include hydroxide,halide, acetate, propionate, decanoate, and stearate ions, with acetateions being preferred anions. The hydroxide form is also preferred.

Instead of being present in the Group IA metal-containing solution,metal ions (including Group IA metal ions) may optionally beincorporated into the ionomer composition of this invention by othermethods. One method is to first saponify a copolymer by the method ofthis invention, then totally or partially replace the ion of thisionomer composition with other metal ions under ion-exchange conditions,or to react the ionomer composition with an aqueous metal hydroxide. Forexample, an ion-exchange solution comprising an aqueous solution of zincoxide or zinc acetate may be mixed with a sodium ionomer composition ofthis invention in a section of a reactive extruder to replace at least aportion of the sodium ions with zinc ions.

Examples of metal ions which may be exchanged include the alkalinemetals, alkaline earth metals such a magnesium, transition metals suchas titanium, cobalt, copper, and zinc, and other metal ions such asaluminum, gallium, germanium, and tin.

The anion of a salt used to ion-exchange the ionomer is preferably onewhich is easily washed out of the ionomer and separated from it duringfiltration. Alternatively, the anion is preferably one which forms aneasily-evolved compound or one which evolves or whose products ofdecomposition evolve at devolatilization conditions in a reactiveextruder. Typical anions include chloride, acetate, propionate,decanoate, and stearate ions. Acetate ions are preferred.

(2) Reactive Extruder

A reactive extruder which is useful in producing compositions of thisinvention comprises an extruder having a copolymer feed section, one ormore reaction sections, a subsequent devolatilization section, and anextrusion section. Typically, these sections are separately jacketed toallow for heating or cooling within each section. These sections canalso be vented with one or more vent ports per section to allow theescape of volatile components, such as the solvent for the Group IAmetal solution and byproducts of the saponification reaction, such asalcohols. Generally, the reactive extruder will also have optional meansfor introducing reactants into any reaction sections as well as meansfor mixing components in the reaction section(s) and means for conveyingthe components through the extruder. Typically, the means for mixing andconveying components to be reacted are screws.

Reactive extruders can have a single screw or multiple screws. Eachscrew typically has a central shaft with a key-way or spline upon whichmixing elements are secured. The reactive extruder may have eitherco-rotating or counter-rotating screws.

Typically, copolymer to be reacted is fed to the screw through aloss-in-weight feeder, and the solid copolymer is melted in a feedsection of the reactive extruder. In some embodiments, all reactants(i.e. copolymer and Group IA metal-containing solution) can be fed tothe reactive extruder through a feed section. In a preferred embodiment,copolymer is introduced into the reactive extruder in a feed section,and the Group IA metal-containing solution is fed to one or morereaction sections. A devolatilization section is a convenient means forremoving any solvent and byproducts of the saponification reaction fromthe saponified composition. Equivalent or additional means for removingvolatile components can be used, however, such as drying the ionomercomposition under reduced pressure in a falling-film evaporator.

One reactive extruder which was particularly effective in producingcompositions of this invention is a Werner-Pfleiderer co-rotating andintermeshing twin-screw extruder. The reactive extruder had a feedsection, a reaction section, a devolatilization section, and apressurization or pumping section which pushed the product through anextrusion die. The devolatilization section had a first portion whichwas vented to a condenser maintained at atmospheric pressure, and asecond portion of the devolatilization section was vented withsufficient vacuum and capacity to remove essentially all of the volatilecomponents from compositions prior to conveying and extruding them.

Typically, copolymer pellets are introduced into a feed section of areactive extruder, where the pellets are heated and worked by the screwto form molten or fluid copolymer. The screw elements also convey themolten copolymer from this feed section to a first reaction section,where the molten copolymer and Group IA metal-containing solution aremixed intensively.

Intensive mixing can be supplied by incorporating one or morereverse-flow elements along with neutral or reverse-flow kneading blockson the screw in a reaction zone. The copolymer to be saponified and theGroup IA metal-containing solution should be mixed as uniformly and asquickly as possible to provide a fairly uniform reaction ofmetal-containing solution with the molten copolymer. Mixing should be ofsufficient intensity that saponification of only localized areas isprevented.

This intensive mixing is of greater intensity than that required in theprior-art processes of U.S. Pat. No. 4,638,034 and U.S. Pat. No.4,042,766. For example, a Werner-Pfleiderer Model ZSK-40 twin-screwreactive extruder had the configuration of screw elements detailed inTable 1 column A. This screw design provided intensive mixing of theGroup IA metal-containing solution with copolymer in the reactionsection through a combination of left-handed elements and neutralkneading blocks. It is believed that the left-handed elements in thereaction section provide momentary retardation of polymer flow inaddition to a shear zone due to impeded and/or reversed flow of thereaction mass, while the neutral kneading blocks imparted intensivemixing and promoted additional shear. Most of the compositions of thisinvention were produced at a screw speed of about 400 to 550 rpm. Highscrew speeds help to assure intensive mixing.

                  TABLE 1                                                         ______________________________________                                        ELEMENT                                                                       NUMBER   COLUMN A    COLUMN B    COLUMN C                                     ______________________________________                                         1       40/20.sup.1 PKR/10.sup.2                                                                              PKR/10                                        2       60/60       20/10       20/10                                         3       60/60       42/42       42/42                                         4       40/40       42/42       42/42                                         5       40/40       42/42       28/28                                         6       40/40       28/28       28/28                                         7       40/20       28/28       28/28                                         8       40/40       20/20       20/20                                         9       25/25       20/20       20/20                                        10       KB45/5/40.sup.3                                                                           20/20       20/20                                        11       KB45/5/40   KB45/5/28   20/10                                        12       25/25       KB45/5/28   KB45/5/28                                    13       25/25       20/20       KB45/5/28                                    14       25/25       20/20       20/20                                        15       40/20 LH.sup.4                                                                            KB90/5/28   20/20                                        16       25/25       20/10 LH    20/10 LH                                     17       KB90/5/40   20/20       20/10 LH                                     18       25/25       20/20       20/10 LH                                     19       KB90/5/40   KB45/5/28   20/20                                        20       25/25       20/10       20/20                                        21       40/20 LH    20/20       KB45/5/28                                    22       25/25       20/20       20/10                                        23       KB90/5/40   KB90/5/28   20/20                                        24       25/25       20/20       20/20                                        25       KB90/5/40   KB45/5/14 LH                                                                              KB90/5/28                                    26       25/25       KB45/5/14 LH                                                                              20/20                                        27       40/20 LH    20/20       KB45/5/14 LH                                 28       KB45/5/20 LH                                                                              20/20       KB45/5/14 LH                                 29       25/25       KB90/5/28   20/20                                        30       25/25       20/20       20/20                                        31       25/25       20/20       KB90/5/28                                    32       25/25       20/20       20/20                                        33       25/25       20/20       20/20                                        34       40/40       20/20       20/20                                        35       40/40       KB90/5/28   20/20                                        36       40/40       20/20       KB90/5/28                                    37       KB45/5/20 LH                                                                              20/20       20/20                                        38       40/40       20/20       20/20                                        39       40/40       20/20       20/20                                        40       40/40       20/20       20/20                                        41       40/40       20/20       KB90/5/28                                    42       25/25       20/20       20/20                                        43       25/25       20/20       20/20                                        44       25/25       KB90/5/28   20/10                                        45       25/25       20/20       20/20                                        46       25/25       20/20       20/20                                        47       25/25       20/10 LH    20/20                                        48       25/25       20/10 LH    20/20                                        49       25/25       20/20       20/20                                        50       25/25       20/20       20/20                                        51       25/25       20/20       20/20                                        52       25/25       20/20       20/20                                        53       25/25       42/42       20/20                                        54       25/25       42/42       20/20                                        55       25/25       42/42       42/42                                        56                   20/20       42/42                                        57                   20/20       42/42                                        58                   20/20       28/28                                        59                   20/20       20/20                                        60                   20/20       20/20                                        61                               20/20                                        ______________________________________                                         NOTES:                                                                        .sup.1 All elements were righthanded elements unless designated otherwise     The first number is the pitch, given in distance (mm) traveled in one         revolution. The second number is the length of the element (mm).              .sup.2 The PKR element is a wedgeshaped adapter which provides a taper        from the  1/2 inch shaft to the first element of the screw.                   .sup.3 KB indicates a kneading block. The first number is the angle forme     by the paddles on the kneading block when compared to the line through th     screw shaft, in degrees. The second number is how many paddles are on one     element. The third number is the length of the element (mm).                  .sup.4 "LH" indicates a lefthanded element.                              

(3) Reaction conditions

Reaction temperature, feed-rate of reactants, and extent ofsaponification are also important processing parameters when makingcompositions of this invention.

(a) Reaction temperature

Compositions of this invention are typically produced where the barreltemperature in the reaction section(s) of the extruder is between about200° and 350° C., although some clear ionomers were prepared at atemperature between about 150° and 200° C. Any reaction temperaturesdiscussed herein refer to the barrel temperatures of the extruder. Theactual temperature of the melted polymer is believed to be lower thanthe measured barrel temperature because of heat-transfer limitations.

Preferably, the reaction temperature is between 225° and 350° C., and,more preferably, the temperature is between about 275° and 350° C. Theupper limit of the temperature range is determined by the temperature atwhich the copolymer or composition degrades. The lower limit of thetemperature range is the temperature at which 1) the copolymer to bereacted is in a molten or fluid state; 2) essentially all of the GroupIA metal in the Group IA metal-containing solution is consumed by thesaponification reaction within the reaction section; and 3) thecomposition being extruded remains visually clear. As a general rule,higher reaction temperatures as specified in the more preferable rangeabove provide low-haze ionomers more consistently than lower reactiontemperatures.

(b) Feed rate of reactants

The Group IA metal-containing solution is fed in an amount that iseffective to achieve the desired extent of saponification of thecopolymer being fed to the reactive extruder. Typically, essentially allof the Group IA metal in solution reacts with the copolymer. The GroupIA metal-containing solution may be fed to a reaction section batch-wiseor continuously, or it may be fed intermittently so that the solution ismixed intimately and rapidly with the molten copolymer. A continuousfeed is preferred. The Group IA metal-containing solution may also besplit between multiple reaction sections and be fed continuously and/orintermittently to any reaction section.

The copolymer to be saponified is fed to the reactive extruder at a ratehigh enough that the molten polymer forms a molten polymer seal betweenconsecutive segments of a reaction section and between a reactionsection and a devolatilization section. This seal can be formed byhaving a reverse-flow screw element at the desired seal location. Thefeed-rate should also be low enough that the reaction mass comprisingthe copolymer to be saponified and the Group IA metal-containingsolution does not move through the reaction section so quickly that thereaction mass is not mixed intensively. The feed-rate should also be lowenough that the extruded polymer is visually clear, corresponding to nomore than ten percent haze.

The copolymer to be saponified may be fed to the extruder batch-wise,intermittently or continuously. A continuous feed is preferred toprovide a commercially-attractive process which is easily andeffectively controlled.

Typically, the average residence time for reactants in a Werner &Pfleiderer ZSK-40 twin-screw extruder which has a feed section, onereaction section, devolatilization section, and pumping section is about30 to about 40 seconds at a continuous feed-rate of approximately 100lb./hr. of polymer to be saponified and at a screw speed of about 500rpm. The average residence time in the reaction section of this reactiveextruder at these conditions is typically about 5 to about 15 seconds.

When the feed-rate is too high to make a composition of this invention,the screw torque will decrease, and the ionomer will turn cloudy. Bothof these conditions can be observed almost immediately upon feeding toomuch copolymer to the extruder. Visually, the extruded copolymer turnsfrom clear to cloudy, and when a strand of the cooled copolymer ispulled in the direction in which it was extruded, the cloudy copolymerturns whitish and opaque.

(c) % saponified

The extent of saponification is defined as the percent of moles ofesters of alpha, beta-ethylenically-unsaturated carboxylic acidsconverted to metal salts of acrylic and methacrylic acid. Compositionsof this invention have been produced where the extent of saponificationof the ester groups in the copolymer has been between about 25 and 99%.Ionomer which has an extent of saponification below about 25% above aretypically cloudy and have poorer gloss, melt strength, and/or tensilestrength than compositions of this invention. A greater extent ofsaponification generally produces low-haze ionomers more consistentlythan a low extent of saponification, particularly when the reactiontemperature is between about 150° and 225° C.

C. Acidification

Acidification of a polymer is a useful method for modifying polymerproperties. In one preferred embodiment, ionomers of this invention haveessentially no acidity. These ionomers can be represented as copolymerscomprising comonomers of alpha-olefins, esters of alpha,beta-ethylenically-unsaturated carboxylic acids, and metal salts ofalpha, beta-ethylenically-unsaturated carboxylic acids. The propertiesof these non-acidic ionomers can be modified by adding acid groups.

Also, some of the ionomers of this invention are highlywater-dispersible. This can be an advantage for applications whererepulpable compositions are desired, such as repulpable paper coatingsand adhesives. However, water dispersibility is a problem where theionomer composition is cooled in a water-bath after saponification,which is a common commercial method of cooling polymers. Much of theionomer to be cooled can end up dispersed in the cooling water, turningthe water a milky white color.

Other cooling means may be used for handling highly water-dispersibleionomers, such as hot-face cutting or utilizing an air-cooled conveyoror a conveyor which has a water-chilled surface to cool the polymerstrands or pellets. However, these methods are more expensive and lessefficient than passing hot polymer in the form of strands, pellets, orfilm through a water bath, and these methods require the installation ofnew equipment in many existing commercial ionomer production facilities.In addition, ionomer may discolor when using these cooling means, sincethe ionomer rapidly oxidizes when it is maintained at elevatedtemperatures for the extended periods of time inherent in these othercooling means.

(1) Cooling ionomer in an aqueous acid bath

In a preferred embodiment, highly water-dispersible ionomer of thisinvention may be cooled in an acid bath to prevent dispersion of much ofthe ionomer. Highly water-dispersible ionomer typically has a highsodium acrylate content which makes the ionomer water-soluble. It isbelieved that ion exchange occurs predominantly on the surface of thepolymer when passing hot ionomer strands through the acid bath,replacing metal ions on the surface of the polymer with hydrogen ionsfrom the acid. It is believed that this makes the surface of the strandsor pellets acidic and substantially reduces their water solubility.

Infrared analysis of ionomer pellets which were cooled in an acid bathdetected no acid groups. However, it is believed that the concentrationof acid groups in the overall ionomer pellets was so small that it wasundetectable by infrared analysis of the bulk ionomer.

Almost any inorganic or water-soluble organic acid can be used in theacid bath. A dilute aqueous solution of a non-oxidizing acid ispreferred to reduce processing cost and to improve the washingefficiency when rinsing any excess acid off of the polymer. Thefollowing list is illustrative of the types of acids which may be used:sulfuric acid, formic acid, propionic acid, oxalic acid, and the like.Preferred acids are hydrochloric acid, phosphoric acid, and acetic acid.

The temperature of the acid solution is preferably that temperaturewhich produces ionomer which has not discolored and which providesionomer at the appropriate temperature for any subsequent processingsteps, such as drying. The temperature of the acid solution is typicallybetween about 5° to 50° C., and preferably is between about 10° and 30°C.

Example 16 illustrates this method for cooling ionomer using an aqueousacid solution.

(2) Acidification of a clear copolymer of ethylene and esters and metalsalts of alpha, beta-ethylenically-unsaturated carboxylic acids

In one embodiment, compositions of this invention have carboxylic acidgroups, in which case the compositions can be represented as copolymerscomprising comonomers of alpha-olefins, esters of alpha,beta-ethylenically-unsaturated carboxylic acids, metal salts of alpha,beta-ethylenically-unsaturated carboxylic acids, and alpha,beta-ethylenically-unsaturated carboxylic acids. Acid groups canplasticize the composition and increase its melt index. This permitstailoring of polymer properties such as polymer flow viscosity, tearstrength, polymer reactivity with food, and odor or taste for aparticular application.

Acidification of a composition comprising a copolymer of alpha-olefins,esters of alpha, beta-ethylenically-unsaturated carboxylic acids, andmetal salts of alpha, beta-ethylenically-unsaturated carboxylic acidscan occur in a reaction section of a reactive extruder. Preferably,acidification occurs in a second reaction section when using reactiveextrusion, and preferably after the composition comprising the reactionproduct of a copolymer of alpha-olefins and esters of alpha,beta-ethylenically-unsaturated carboxylic acids has been saponified witha Group IA metal-containing solution in a first reaction section.

Other equipment may be used in place of a reactive extruder foracidification of a saponified composition. For example, a BrabenderPlasticorder, a resin kettle, or an autoclave may be used.

A non-oxidizing acid can be used at a temperature and in a concentrationwhich does not cause significant degradation of the copolymer orcomposition. Typically, the amount of acid required is the amount whichprovides the desired weight percent of acid groups per combined weightof acid and copolymer to be acidified. Examples of these acids includephosphoric acid, hydrochloric acid, benzoic acid, lactic acid, andstearic acid. Polymeric non-oxidizing acids can also be used, such asethylene-acrylic acid copolymer, exemplified by Dow Chemical Company'sPrimacor Grade 3330. The non-oxidizing acids may have only one or twomonomer units, such as benzoic acid or acetic acid, or they may comprisepolymeric acids having multiple monomer units and having a molecularweight well in excess of one million, such as Primacor Grade 3330.Phosphoric acid, lactic acid, and polymer acids are preferred. Typicaltemperatures for acidification are between about 190° and 300° C., andpreferably are between about 230° and 300° C. The acid concentration ispreferably between 10 and 95%.

In certain applications or compositions of this invention, anybyproducts of acidification can remain in the composition. For otherapplications or compositions, any byproducts of acidification and/or anyexcess acid can be removed from the ionomer by washing with water orother solvent and filtering the composition. For example, polymeracidified using phosphoric acid can be washed with water in anautoclave. The byproduct salt in the aqueous phase can subsequently beseparated from the polymer by filtration.

D. Uses of the compositions

Ionomer compositions of this invention can be formed into single ormulti-layer films using conventional equipment. For example, cast,extruded, or blown film can be made.

An ionomer composition of this invention can be coextruded with orlaminated to other polymers such as nylon (unoriented and oriented),polyester (unoriented and oriented), polystyrene, polyvinyl acetate,polyacrylonitrile, polyvinylidene dichloride, and polyolefins such aspolypropylene (unoriented and oriented), polyethylene (low density, highdensity, and linear low density), ethylene-methyl (meth)acrylatecopolymers, ethylene-ethyl (meth)acrylate copolymers,ethylene-(meth)acrylic acid copolymers, ethylene-vinyl alcoholcopolymers, ethylene vinyl acetate copolymers, and other polymers andtheir derivatives capable of being coextruded. Typical uses for ionomercompositions of this invention include their use in single-layer ormulti-layer films, where they can be used as tie layers or used forimparting flexibility, toughness, strength, hot tack, and/or heat sealcapabilities. Such uses include stretch films, bundling (shrink) wrap,food and drug packaging, and skin packaging for protecting the contentsof a package. A layer of ionomer of this invention can withstand highertemperatures encountered in some end-uses, such as cook-in bags orautoclave sterilization. Also, the ionomer of this invention has highadhesion to other organic materials such as other polymers or evennatural polymers such as the protein found in meat and cheese.

Single-layer ionomer film or multi-layer film in which the ionomer is onone face of the film can be used as a surface protection layer forproducts such as glass, polycarbonate or poly(methyl methacrylate)products, which can be used in windshields for vehicles or windows. Theionomer layer protects products from scratches and/or nicks because ofthe ionomer's abrasion resistance. The ionomer's adhesion to suchsubstrates is excellent, yet it can be peeled readily from the surface.The transparency of the ionomer of this invention allows visualinspection of the surface of the wrapped product, permitting a customerto inspect a product for flaws prior to receipt and unwrapping of theproduct.

Ionomer of this invention can also be used as a glass inter-layer. Theionomer provides shatter resistance, sound dampening, and/orbullet-proof characteristics to the glass structure incorporating theionomer.

Single-layer ionomer film or multi-layer film containing ionomer of thisinvention can be used to make easy-open packaging such as easy-tearfilm, bags, pouches and parcels. A tear propagates linearly through thefilm, both in the machine and transverse directions in blown and castfilms, and the Elmendorf tear strength of the ionomer indicates that itis well-suited to uses such as easy-opening packaging. The package inwhich the film is incorporated normally is notched or incorporates atear strip to facilitate ease of opening of the package.

The ionomer of this invention can also serve as its own tie layer due toits good adhesion to other layers. This eliminates the need for separatetie layers in a multi-layer film, reducing the thickness of themulti-layer film and reducing the overall cost of making the multi-layerfilm.

Ionomer of this invention can be blended with other polymers to modifythe properties of the ionomer and/or the polymer with which it isblended. Ionomer of this invention forms compatible blends with manypolymers. The ionomer can improve processability of polymers such asethylene-vinyl alcohol copolymer and polyesters. Ionomer can be used toadjust many properties of the blended composition, such as theelasticity, impact resistance, amount of shrinkage of polymer used ininjection-molding, softness, flexibility, heat seal, hot tack, andbrittleness, and can be used in those applications where ionomer aloneis used.

The ionomer of this invention can also be used alone or in combinationwith other polymers to make peelable seals.

Polymers with which the ionomer of this invention may be blended includeethylene-acrylic acid and -methacrylic acid copolymers; other ionomerssuch as ethylene-acrylic acid and -methacrylic acid ionomers partiallyneutralized with sodium, zinc, lithium, and/or other cations; ethylenealkyl acrylate and methacrylate copolymers, including ethylene-methylacrylate copolymer, ethylene-methyl methacrylate copolymer,ethylene-ethyl acrylate copolymer and ethylene-butyl acrylate copolymer;ethylene-vinyl acetate copolymer; polyolefins, including low, linearlow, medium and high-density polyethylene, polypropylene, andpolybutadiene; ethylene vinyl alcohol copolymer; polyamides, includingnylon 6, nylon 12 and nylon 6,6; polyesters, including poly(ethyleneterephthalate); polycarbonates; polystyrene, including high-impactpolystyrene, acrylonitrile-butadiene-styrene copolymer, and blockcopolymers of styrene and butadiene; poly(vinyl chloride); polyurethane;and epoxy resins.

Ionomer of this invention blends well with ethylene alkyl acrylateand/or methacrylate copolymers. The ionomer and copolymer formcompatible blends, where there is little or no phase separation.Blending permits tailoring the heat seal and hot tack properties forparticular uses.

Ionomer of this invention may also be cross-linked to other polymersthat have reactive groups. Cross-linking can be achieved by irradiation,by organic peroxide-induced cross-linking, or via acidolysis ortransesterification. In this manner, properties such as melt-pointtemperature, processability, elasticity, impact resistance, amount ofshrinkage of polymer used in injection-molding, softness, flexibility,heat seal, hot tack, and brittleness may be further modified. A polymerhaving a reactive group is one typically formed by reacting bi- or tri-or multi-functional monomers to form polymers having at least onefunctional (i.e. reactive) group on the side and/or end of the polymerbackbone. The reactive group is one that is capable of participating inan acidolysis or a transesterification reaction.

Examples of polymers with which ionomer of this invention may becross-linked through reactive groups via acidolysis include polyesters,such as poly(ethylene terephthalate), polyamides, such as nylon 6 andnylon 6,6, polyurethanes, and polycarbonates. In these polymers, thefunctional or reactive group is an amine or a carboxyl group. Examplesof polymers with which ionomer of this invention may be cross-linkedthrough a reactive group via transesterification include polyesters andethylene-alkyl acrylate and -methacrylate copolymers. In these polymers,the functional or reactive group is a carboxyl group or an ester.

Cross-linking may occur in any equipment suitable to acidify ortransesterify the polymers. A twin-screw reactive extruder can be usedto form a melt blend of the ionomer and polymer with which the ionomerwill be linked and to perform the acidification or transesterification.The acid or transesterification catalyst may be fed to the extruder withthe ionomer and polymer to which the ionomer is to be linked, and/or theacid or transesterification catalyst may be fed directly to a reactionzone of the reactive extruder. Many acids may be used in theacidification reaction, but preferably the acid is a weak organic acidsuch as carbonic or acetic acid. Any transesterification catalyst may beused, but preferably the catalyst is a titanate such as tetraethyltitanate. A reactive extruder typically has a devolatilization sectionto remove volatile byproducts of acidification or transesterification,and if desired, the reacted blend may also be treated with a high pHcompound such as sodium hydroxide or soda ash to remove any excessacidity after acidification. The properties of a blend of ionomer andother polymers can thus be further modified by cross-linking the blend.

Ionomer compositions of this invention may also be used in thermallyextruded and thermally formed products such as automotive interior partsand skin packaging. The ionomer compositions may be used alone or incombination with other polymers in blow-molded or injection moldedarticles, particularly where such articles need to be grease- andoil-resistant such as bottles for fragrances or detergents, and thecompositions may also be used in articles such as food trays formed byvacuum thermo-forming. The ionomer compositions of this invention may beused in making articles such as golf ball covers; coated fabrics;orthopedic, prosthetic and medical devices; recreational equipment; andfootwear components. The ionomer compositions of this invention areespecially useful in applications where the ionomer properties discussedabove, as well as the excellent abrasion resistance, transparency,and/or directional tear properties of the ionomer, are useful.

Theories discussed herein are intended to provide possible explanationsfor what was observed. These theories are not to be interpreted aslimiting the invention described herein. Also, the following examplesare illustrative and are not intended to limit the invention disclosedherein.

EXAMPLE 1

An ethylene-methyl acrylate copolymer (manufactured by Chevron by themethod disclosed in U.S. Pat. No. 3,350,372) containing 20% by weightmethyl acrylate (7.5 mole %) and having a melt index of 400 g/10 min.(190° C.) was fed to a Werner & Pfleiderer corrosion-resistant ZSK-40mmtwin screw extruder at a rate of 100 lbs./hr. The extruder had a ratioof length to diameter of about 44. The screw configuration for Examples1-13 and Comparative Example A is given in Table 1 column A. Aqueoussodium hydroxide (50% NaOH by weight in all examples, except where notedotherwise) was fed to Zone 3 of the extruder at 9.3 lbs./hr. The screwspeed was 550 rpm.

The following extruder temperatures were measured:

                  TABLE 2                                                         ______________________________________                                        Zone No. 1      2      3     4    5     6    7                                ______________________________________                                        Temperature                                                                            236    350    253   253  230   245  260                              (°C.)                                                                  ______________________________________                                         Note:                                                                         Zone 1: melting section for polymer to be reacted;                            Zone 2 & 3: reaction section;                                                 Zone 4: devolatilization section;                                             Zones 5-7: extrusion section.                                            

Water from the sodium hydroxide solution and the reaction by-productmethanol were removed by a two-stage devolatilization. In all examples,the evolved water and methanol from the first devolatilization stagewere condensed at atmospheric pressure. The second devolatilizationstage was connected to a vacuum system in all examples. The seconddevolatilization stage had 28.4 in. Hg vacuum during this run.

The reaction product was extruded through an eight-strand die, cooled ona stainless steel belt (about 20 feet in length, made by Sandvik) whichwas chilled by cold water underneath the belt, and subsequentlypelletized.

The product had a melt flow rate of 0.33 g/10 min. (230° C.). Theproduct had a hydrolysis of 53% (i.e., 53% of the methyl acrylate in theethylene-methyl acrylate copolymer was converted to sodium acrylate).

The polymer was made into blown film on a Victor blown film line at thefollowing processing conditions:

                                      TABLE 3                                     __________________________________________________________________________                             Die  Melt                                            Zone 1                                                                            Zone 2                                                                            Zone 3                                                                            Adapter                                                                            Die 1                                                                             Die 2                                                                             Pressure                                                                           Temperature                                     __________________________________________________________________________    400° F.                                                                    440° F.                                                                    515° F.                                                                    435° F.                                                                     430° F.                                                                    440° F.                                                                    7600 psi                                                                           440° F.                                  __________________________________________________________________________

The blown film had a thickness of 3.5 mils. The haze of the film was 2%,and the 60° gloss was 122. The 1% secant moduli of the film were 12,740and 10,080 psi respectively for the machine direction (MD) and thetransverse direction (TD).

All haze values were measured using the method of ASTM D 1003. The 60°gloss values were measured using the method of ASTM D 2457. The 1%secant modulus values and tensile strength values were measured usingthe method of ASTM D-638.

Melt index of feed resin was measured by the method of ASTM D 1239,using a temperature of 190° C. and a 2.16 kg weight. The melt flow rateof a composition of this invention was determined by the method of ASTMD 1239 but using a temperature of 230° C. rather than 190° C. and usinga 2.16 kg weight.

The hydrolysis of the product is defined as the moles of metal salt ofthe alpha, beta-ethylenically-unsaturated carboxylic acid present in theproduct, expressed as a percentage of the moles of the ester of alpha,beta-ethylenically-unsaturated carboxylic acid present prior tosaponifying the copolymer. The terms "hydrolysis", "extent ofhydrolysis", "percent hydrolysis", "percent saponified", and "extent ofsaponification" are used interchangeably.

The extent of hydrolysis is determined by dissolving 10 g. of ionomer in250 ml. of tetrahydrofuran (THF) in a 500 ml. round-bottom flask, towhich 1 ml. of glacial acetic acid is added. The flask is fitted with arefluxing condenser, and the contents are boiled for about 20 min. Themixture is poured into 1 liter of cold distilled water (about 15-°20°C.), and then filtered. The precipitate is subsequently washed withabout 3 liters of distilled water. The precipitate is dried undervacuum, then weighed and dissolved in THF and titrated with 0.1Npotassium hydroxide in ethanol, using thymol blue to indicate theend-point of titration. The extent of hydrolysis is then calculated bydividing the moles of potassium used in titrating the sample by themoles of ester present in the initial ethylene-methyl acrylate copolymerprior to the saponification reaction.

EXAMPLE 2

The ethylene-methyl acrylate copolymer of Example 1 was fed to theWerner & Pfleiderer corrosion-resistant ZSK-40 mm twin screw extruder ata rate of 100 lbs./hr. Aqueous sodium hydroxide was fed to Zone 3 of theextruder at a rate of 11.2 lbs./hr. The screw speed was 500 rpm.

The following temperatures were measured during the process:

                  TABLE 4                                                         ______________________________________                                        Zone No. 1      2      3     4    5     6    7                                ______________________________________                                        Temperature                                                                            271    252    255   256  230   231  241                              (°C.)                                                                  ______________________________________                                    

The vacuum on the second devolatilization zone was 28.4 in. Hg. Thereaction product was extruded, cooled on a Sandvik belt and pelletizedin the same way as Example 1. The product had a melt flow rate of 0.20g/10 min. (230° C.). The hydrolysis of the product was 65%.

The polymer was made into blown film on a Victor blown film line usingthe processing conditions similar to those in Example 1. The haze of theblown film was 2%, and the 60° gloss was 133. The film had a tensilestrength of 4010 and 3180 psi respectively for MD and TD. The 1% secantmoduli of the film were 14720 and 13110 psi respectively for MD and TD.

EXAMPLE 3

The ethylene-methyl acrylate copolymer of Example 1 was fed to theWerner & Pfleiderer corrosion-resistant ZSK-40 mm twin screw extruder ata rate of 100 lbs./hr. Aqueous sodium hydroxide was fed to Zone 3 on theextruder at a rate of 12.1 lbs./hr. The screw speed was 500 rpm.

The following temperatures were measured during the process:

                  TABLE 5                                                         ______________________________________                                        Zone No. 1      2      3     4    5     6    7                                ______________________________________                                        Temperature                                                                            218    347    255   255  230   251  260                              (°C.)                                                                  ______________________________________                                    

The vacuum on the second devolatilization zone was 28.5 in. Hg. Thereaction product was extruded, cooled on a Sandvik belt and pelletizedin the same way as Example 1. The product had a melt flow rate of 0.1g/10 min. (230° C.). The hydrolysis of the product was 70%.

The polymer was made into blown film on a Victor blown film line usingthe processing conditions similar to those in Example 1. The haze of theblown film was 2%, and the 60° gloss was 134. The film had a tensilestrength of 4470 and 2420 psi respectively for MD and TD.

EXAMPLE 4

An ethylene-methyl acrylate copolymer containing 20% by weight methylacrylate and having a melt index of 570 g/10 min. (190° C.) was fed tothe Werner & Pfleiderer corrosion-resistant ZSK-40 mm twin screwextruder at a rate of 100 lbs./hr. Aqueous sodium hydroxide was fed toZone 3 on the extruder at a rate of 13.0 lbs./hr. The screw speed was500 rpm.

The following temperatures were measured during the process:

                  TABLE 6                                                         ______________________________________                                        Zone No. 1      2      3     4    5     6    7                                ______________________________________                                        Temperature                                                                            178    242    254   252  301   303  289                              (°C.)                                                                  ______________________________________                                    

The vacuum on the second devolatilization zone was 25.5 in. Hg. Thereaction product was extruded, cooled on a Sandvik belt and pelletizedin the same way as Example 1. The product had a melt flow rate of 0.87g/10 min. (230° C.). The hydrolysis of the product was 69%.

The polymer was made into blown film on a Victor blown film line usingthe processing conditions similar to those in Example 1. The haze of theblown film was 2%, and the 60° gloss (ASTM D 2457) was 135. The film hada tensile strength of 2870 and 1760 psi respectively for MD and TD.

EXAMPLE 5

An ethylene-methyl acrylate copolymer containing 20% by weight methylacrylate and having a melt index of 440 g/10 min. (190° C.) was fed tothe Werner & Pfleiderer corrosion-resistant ZSK-40 mm twin screwextruder at a rate of 100 lbs./hr. Aqueous sodium hydroxide was fed toZone 3 on the extruder at a rate of 13.0 lbs./hr. The screw speed was500 rpm.

The following temperatures were measured during the process:

                  TABLE 7                                                         ______________________________________                                        Zone No. 1      2      3     4    5     6    7                                ______________________________________                                        Temperature                                                                            189    257    257   258  251   263  283                              (°C.)                                                                  ______________________________________                                    

The vacuum on the second devolatilization zone was 28.4 in. Hg. Thereaction product was extruded, cooled on a Sandvik belt and pelletizedin the same way as Example 1. The product had a melt flow rate of 0.81g/10 min. (230° C.). The hydrolysis of the product was 72%.

The polymer was made into blown film on a Victor blown film line usingthe processing conditions similar to those in Example 1. The haze of theblown film was 2%, and the 60° gloss was 135. The film had a tensilestrength of 2600 and 1850 psi respectively for MD and TD.

EXAMPLE 6

An ethylene-methyl acrylate copolymer containing 23% by weight methylacrylate and having a melt index of 500 g/10 min. (190° C.) was fed tothe Werner & Pfleiderer corrosion-resistant ZSK-40 mm twin screwextruder at a rate of 100 lbs./hr. Aqueous sodium hydroxide was fed toZone 3 on the extruder at a rate of 10.7 lbs./hr. The screw speed was500 rpm.

The following temperatures were measured during the process:

                  TABLE 8                                                         ______________________________________                                        Zone No. 1      2      3     4    5     6    7                                ______________________________________                                        Temperature                                                                            181    247    256   255  255   254  270                              (°C.)                                                                  ______________________________________                                    

The vacuum on the second devolatilization zone was 26.7 in. Hg. Thereaction product was extruded, cooled on a Sandvik belt and pelletizedin the same way as Example 1. The product had a melt flow rate of 0.54g/10 min. (230° C.). The hydrolysis of the product was 51%.

The polymer was made into blown film on a Victor blown film line usingthe processing conditions similar to those in Example 1. The haze of theblown film was 2%, and the 60° gloss was 124. The film had a tensilestrength of 2270 and 1470 psi respectively for MD and TD.

EXAMPLE 7

An ethylene-methyl acrylate copolymer containing 23% by weight methylacrylate and having a melt index of 500 g/10 min. (190° C.) was fed tothe Werner & Pfleiderer corrosion-resistant ZSK-40 mm twin screwextruder at a rate of 100 lbs./hr. Aqueous sodium hydroxide was fed toZone 3 on the extruder at a rate of 12.8 lbs./hr. The screw speed was500 rpm.

The following temperatures were measured during the process:

                  TABLE 9                                                         ______________________________________                                        Zone No. 1      2      3     4    5     6    7                                ______________________________________                                        Temperature                                                                            175    247    253   259  254   257  271                              (°C.)                                                                  ______________________________________                                    

The vacuum on the second devolatilization zone was 26.6 in. Hg. Thereaction product was extruded, cooled on a Sandvik belt and pelletizedin the same way as Example 1. The product had a melt flow rate of 0.45g/10 min. (230° C.). The hydrolysis of the product was 61%.

The polymer was made into blown film on a Victor blown film line usingthe processing conditions similar to those in Example 1. The haze of theblown film was 3%, and the 60° gloss was 132. The film had a tensilestrength of 2730 and 1960 psi respectively for MD and TD.

EXAMPLE 8

An ethylene-methyl acrylate copolymer containing 23% by weight methylacrylate and having a melt index of 500 g/10 min. (190° C.) was fed tothe Werner & Pfleiderer corrosion-resistant ZSK-40 mm twin screwextruder at a rate of 100 lbs./hr. Aqueous sodium hydroxide was fed toZone 3 on the extruder at a rate of 9.6 lbs./hr. The screw speed was 500rpm.

The following temperatures were measured during the process:

                  TABLE 10                                                        ______________________________________                                        Zone No. 1      2      3     4    5     6    7                                ______________________________________                                        Temperature                                                                            193    284    257   259  254   254  271                              (°C.)                                                                  ______________________________________                                    

The vacuum on the second devolatilization zone was 26.2 in. Hg. Thereaction product was extruded, cooled on a Sandvik belt and pelletizedin the same way as Example 1. The product had a melt flow rate of 0.60g/10 min. (230° C.). The hydrolysis of the product was 46%.

The polymer was made into blown film on a Victor blown film line usingthe processing conditions similar to those in Example 1. The haze of theblown film was 2%, and the 60° gloss was 120. The film had a tensilestrength of 1950 and 1240 psi respectively for MD and TD.

EXAMPLE 9

An ethylene-methyl acrylate copolymer containing 22% by weight methylacrylate and having a melt index of 470 g/10 min. (190° C.) was fed tothe Werner & Pfleiderer corrosion-resistant ZSK-40 mm twin screwextruder at a rate of 100 lbs./hr. Aqueous sodium hydroxide was fed toZone 3 on the extruder at a rate of 14.3 lbs./hr. The screw speed was500 rpm.

The following temperatures were measured during the process:

                  TABLE 11                                                        ______________________________________                                        Zone No. 1      2      3     4    5     6    7                                ______________________________________                                        Temperature                                                                            298    326    255   266  254   254  271                              (°C.)                                                                  ______________________________________                                    

The vacuum on the second devolatilization zone was 28.4 in. Hg. Thereaction product was extruded, cooled on a Sandvik belt and pelletizedin the same way as Example 1. The product had a melt flow rate of 0.23g/10 min. (230° C.). The hydrolysis of the product was 70%.

The polymer was made into blown film on a Victor blown film line usingthe processing conditions similar to those in Example 1. The haze of theblown film was 1%, and the 60° gloss was 134. The film had a tensilestrength of 3000 and 2170 psi respectively for MD and TD.

EXAMPLE 10

An ethylene-methyl acrylate copolymer containing 23% by weight methylacrylate and having a melt index of 500 g/10 min. (190° C.) was fed tothe Werner & Pfleiderer corrosion-resistant ZSK-40 mm twin screwextruder at a rate of 100 lbs./hr. Aqueous sodium hydroxide was fed toZone 3 on the extruder at a rate of 8.6 lbs./hr. The screw speed was 500rpm.

The following temperatures were measured during the process:

                  TABLE 12                                                        ______________________________________                                        Zone No. 1      2      3     4    5     6    7                                ______________________________________                                        Temperature                                                                            177    262    255   253  254   255  270                              (°C.)                                                                  ______________________________________                                    

The vacuum on the second devolatilization zone was 25.8 in. Hg. Thereaction product was extruded, cooled on a Sandvik belt and pelletizedin the same way as Example 1. The product had a melt flow rate of 1.25g/10 min. (230° C.). The hydrolysis of the product was 41%.

The polymer was made into blown film on a Victor blown film line usingthe processing conditions similar to those in Example 1. The haze of theblown film was 4%, and the 60° gloss was 104. The film had a tensilestrength of 1910 and 970 psi respectively for MD and TD.

EXAMPLE 11

An ethylene-methyl acrylate copolymer containing 20% by weight methylacrylate and having a melt index of 100 g/10 min. (190° C.) was fed tothe Werner & Pfleiderer corrosion-resistant ZSK-40 mm twin screwextruder at a rate of 100 lbs./hr. Aqueous sodium hydroxide was fed toZone 3 on the extruder at a rate of 4.7 lbs./hr. The screw speed was 500rpm.

The following temperatures were measured during the process:

                  TABLE 13                                                        ______________________________________                                        Zone No. 1      2      3     4    5     6    7                                ______________________________________                                        Temperature                                                                            253    322    254   230  230   231  241                              (°C.)                                                                  ______________________________________                                    

The vacuum on the second devolatilization zone was 28.4 in. Hg. Thereaction product was extruded, cooled on a Sandvik belt and pelletizedin the same way as Example 1. The product had a melt flow rate of 0.67g/10 min. (230° C.). The hydrolysis of the product was 26%.

The polymer was made into blown film on a Victor blown film line usingthe processing conditions similar to those in Example 1. The haze of theblown film was 3%, and the 60° gloss was 115. The film had a tensilestrength of 1150 and 1080 psi respectively for MD and TD.

EXAMPLE 12

An ethylene-methyl acrylate copolymer containing 20% by weight methylacrylate and having a melt index of 400 g/10 min. (190° C.) was fed tothe Werner & Pfleiderer corrosion-resistant ZSK-40 mm twin screwextruder at a rate of 100 lbs./hr. Aqueous sodium hydroxide was fed toZone 3 on the extruder at a rate of 9.3 lbs./hr. The screw speed was 500rpm.

The following temperatures were measured during the process:

                  TABLE 14                                                        ______________________________________                                        Zone No. 1      2      3     4    5     6    7                                ______________________________________                                        Temperature                                                                            209    201    266   255  256   256  256                              (°C.)                                                                  ______________________________________                                    

The vacuum on the second devolatilization zone was 24.7 in. Hg. Thereaction product was extruded, cooled in a water bath, and pelletized.The pellets were dried in a vacuum over at 65° C. and 29.5 in. Hg for 48hours. The product had a melt flow rate of 0.66 g/10 min. (230° C.). Thehydrolysis of the product was 49%.

The polymer was made into blown film on a Victor blown film line usingthe processing conditions similar to those in Example 1. The haze of theblown film was 3%, and the 60° gloss was 128.

EXAMPLE 13

An ethylene-methyl acrylate copolymer containing 20% by weight methylacrylate and having a melt index of 150 g/10 min. (190° C.) was fed tothe Werner & Pfleiderer corrosion-resistant ZSK-40 mm twin screwextruder at a rate of 100 lbs./hr. Aqueous sodium hydroxide was fed toZone 3 on the extruder at a rate of 7.4 lbs./hr. The screw speed was 450rpm.

The following temperatures were measured during the process:

                  TABLE 15                                                        ______________________________________                                        Zone No. 1      2      3     4    5     6    7                                ______________________________________                                        Temperature                                                                            188    199    276   253  257   260  262                              (°C.)                                                                  ______________________________________                                    

The vacuum on the second devolatilization zone was 28.5 in. Hg. Thereaction product was extruded, cooled in a water bath, and pelletized.The pellets were dried in a vacuum over at 65° C. and 29.5 in. Hg for 48hours. The product had a melt flow rate of 0.22 g/10 min. (230° C.). Thehydrolysis of the product was 42%.

The polymer was made into blown film on a Victor blown film line usingthe processing conditions similar to those in Example 1. The haze of theblown film was 4%, and the 60° gloss was 122.

EXAMPLE 14

An ethylene-methyl acrylate copolymer containing 20% by weight methylacrylate and having a melt index of 400 g/10 min. (190° C.) was fed to aWerner & Pfleiderer ZSK-58 mm twin screw extruder at a rate of 425lbs./hr. The screw was configured to provide substantially the samemixing as provided in the ZSK-40 mm extruder in Examples 1-13. Aqueoussodium hydroxide was fed to the reaction zone on the extruder at a rateof 56 lbs./hr.

The screw speed of the extruder was at 500 rpm. The temperatures in thereaction zones were 226° C. to 338° C. The product was 71% hydrolyzed.The product had similar optical properties to the product of Example 3.

EXAMPLE 15

An ethylene-methyl acrylate copolymer containing 20% by weight methylacrylate and having a melt index of 400 g/10 min. (190° C.) was fed to aWerner & Pfleiderer ZSK-70 mm twin screw extruder at a rate of 450lbs./hr. The screw was configured to provide substantially the samemixing as provided in the ZSK-40 mm extruder in Examples 1-13. Aqueoussodium hydroxide was fed to the reaction zone on the extruder at a rateof 50 lbs./hr.

The screw speed of the extruder was at 580 rpm. The temperatures in thereaction zones were 330° C. to 350° C. The product was 61% hydrolyzed.The product had similar optical properties to the product of Example 3.

COMPARATIVE EXAMPLE A

An ethylene-methyl acrylate copolymer containing 20% by weight methylacrylate and having a melt index of 20 g/10 min. (190° C.) was fed tothe Werner & Pfleiderer corrosion-resistant ZSK-40 mm twin screwextruder at a rate of 100 lbs./hr. Aqueous sodium hydroxide was fed toZone 3 on the extruder at a rate of 4.6 lbs./hr. The screw speed was 400rpm.

The following temperatures were measured during the process:

                  TABLE 16                                                        ______________________________________                                        Zone No. 1      2      3     4    5     6    7                                ______________________________________                                        Temperature                                                                            216    213    270   269  270   271  270                              (°C.)                                                                  ______________________________________                                    

The vacuum on the second devolatilization zone was 27.9 in. Hg. Thereaction product was extruded, cooled in a water bath, and pelletized.The pellets were dried in a vacuum over at 65° C. and 29.5 in. Hg for 48hours. The product had a melt flow rate of 3.2 g/10 min. (190° C.). Thehydrolysis of the product was 15%.

The polymer was made into blown film on a Victor blown film line usingthe processing conditions similar to those in Example 1. The haze of theblown film was 81%, and the 60° gloss was 35.

This Comparative Example A shows that saponifying 15% of the methylacrylate groups to form the sodium salt of acrylic acid is insufficientat these reaction conditions to produce the low haze of compositions ofthis invention.

COMPARATIVE EXAMPLE B

An ethylene-methyl acrylate copolymer containing 20% methyl acrylate byweight and having a melt index of 400 g/10 min. was fed to a Werner &Pfleiderer ZSK-30 corrosion-resistant extruder at 13.2 lbs/hr. 1.73lbs/hr. of 35% sodium hydroxide solution was fed to zone 3 of theextruder. The extruder had the configuration of elements shown in Table1 column B.

The following extruder temperatures were measured:

                  TABLE 17                                                        ______________________________________                                        Zone No. 1      2      3     4    5     6    7                                ______________________________________                                        Temperature                                                                            230    275    275   275  275   240  235                              (°C.)                                                                  ______________________________________                                    

Water and the by-product methanol were removed in a two-stagedevolatilization zone. The polymer strands were cooled in a water bathand pelletized. The pellets were vacuum-dried overnight at about 25 in.Hg vacuum and at 68° C.

Chemical analysis of the product indicated a degree of saponification of49.2%. The product had a melt index (190° C.) of 0.54 g/10 min.

A 1/2 inch Randcastle miniextruder was used to make a cast film of about4 inch width. The temperature at the feed zone and barrels 1A through 3Awas 430° C., while the die temperature was 440° C. The film had a hazeof 55% and a 60° gloss of 20.

It is believed that the poor clarity of this example results from a moredilute caustic solution and poorer mixing at these reaction conditionsas compared to the conditions which produce compositions of thisinvention.

COMPARATIVE EXAMPLE C

An ethylene-methyl acrylate copolymer containing 20% methyl acrylate byweight and having a melt index of 400 g/10 min. was fed to a Werner &Pfleiderer ZSK-30 corrosion-resistant extruder at 13.2 lbs/hr. 2.29lbs/hr. of 35% sodium hydroxide solution was fed to zone 3 of theextruder. The extruder had the configuration of elements shown in Table1 column B.

The following extruder temperatures were measured:

                  TABLE 18                                                        ______________________________________                                        Zone No. 1      2      3     4    5     6    7                                ______________________________________                                        Temperature                                                                            230    275    275   275  275   240  235                              (°C.)                                                                  ______________________________________                                    

Water and the by-product methanol were removed in a two-stagedevolatilization zone. The polymer strands were cooled in a water bathand pelletized. The pellets were vacuum-dried overnight at about 25 in.Hg vacuum and at 68° C.

Chemical analysis of the product indicated a degree of saponification of65.2%. The product had a melt flow rate of 0.38 g/10 min. (230° C.).

A 1/2 inch Randcastle miniextruder was used to make a cast film of about4 inch width. The temperature at the feed zone and barrels 1A through 3Awas 430° C., while the die temperature was 440° C. The film had a hazeof 15% and a 60° gloss of 66.

This comparative example shows that a greater extent of hydrolysisprovided clearer ionomer, but mixing conditions as supplied by the screwdesign of Table 1 column B when using 35% aqueous caustic did not appearto provide the intensive mixing and reaction conditions necessary toobtain a haze of 10% or less.

COMPARATIVE EXAMPLE D

Ethylene-methyl acrylate copolymer having 20 weight percent methylacrylate and a 400 melt index (190° C.) was saponified with a 35% byweight aqueous solution of sodium hydroxide per the method ofComparative Example B. The product was 60% saponified and had a meltindex (190° C.) of 0.06. The tensile strength in the machine directionwas 1582 psi.

COMPARATIVE EXAMPLE E

Ethylene-methyl acrylate copolymer having 25 weight percent methylacrylate and a 457 melt index (190° C.) was saponified with a 35% byweight aqueous solution of sodium hydroxide per the method ofComparative Example B. The product was 44% saponified and had a meltindex (190° C.) of 0.04. The tensile strength in the machine directionwas 985 psi.

EXAMPLE 16 Acid Bath Cooling of Ionomer

26.4 lbs./hr. of the ethylene-methyl acrylate copolymer of Example 1were fed to a Werner & Pfleiderer corrosion resistant ZSK-30 twin-screwextruder having the configuration of elements given in Table 1 column C.50% aqueous sodium hydroxide was fed into zone 3 at 2.5 lb./hr. Thescrew speed was 500 rpm.

The following extruder temperatures were measured:

                  TABLE 19                                                        ______________________________________                                        Zone No. 1      2      3     4    5     6    7                                ______________________________________                                        Temperature                                                                            174    200    255   260  254   267  255                              (°C.)                                                                  ______________________________________                                    

Volatile components were removed in a two port devolatilization section,and the second port had a vacuum of 28 in. Hg. The polymer strands froma four-strand die were cooled in a 5% phosphoric acid bath which was 10ft. long, and were then rinsed in a 2 ft. water bath and pelletized in aConair pelletizer.

During 1.75 hours of operation, the ionomer was efficiently cooled andpelletized, and the acid bath remained acidic and clear with no evidenceof dissolved polymer. Total carbon analysis of the cooling water(determined by potentiometric titration) at the end of operation showedless than 20 ppm of dissolved carbon. By contrast, when the same polymerwas cooled in water, the water bath became turbid and milky-white withina few minutes of operation.

The resulting pellets were colorless, shiny, and clear.

EXAMPLE 17

This example shows a copolymer of ethylene, methyl acrylate, sodiumacrylate, and acrylic acid. First, ethylene-methyl acrylate copolymerhaving 20 weight percent methyl acrylate and 153 melt index (190° C.)was saponified in a Werner-Pfleiderer ZSK-30 twin-screw reactiveextruder using 50% aqueous sodium hydroxide and substantially the samereaction conditions as Example 16. The extent of saponification was 42%.The pelletized ionomer was clear and glossy and had a melt flow rate(230° C.) of 0.17 g/10 min.

The ionomer pellets were fed to the extruder at a rate of 12 kg/hr.85.6% aqueous phosphoric acid was fed to Zone 3 of the extruder at arate of 0.14 kg/hr., and the product was extruded, cooled in a waterbath, and pelletized.

The product retained its clear and glossy optical properties, and themelt flow rate increased to 1.0 g/10 min. (230° C.). Film that was madeon the Randcastle mini-extruder had a tensile strength in the machinedirection of 2418 psi.

EXAMPLE 18

Ethylene-methyl acrylate copolymer having 20 weight percent methylacrylate and 400 melt index (190° C.) was saponified in a ZSK-30extruder having the configuration of elements given in Table 1 column Cwith 50% aqueous sodium hydroxide at a reaction temperature of about148° C. The screw speed was 500 rpm. The copolymer was fed to theextruder at a rate of 12 kg/hr., and the product was about 54%saponified. The product was visually clear.

COMPARATIVE EXAMPLE F

Ethylene-methyl acrylate copolymer having 20 weight percent methylacrylate and 400 melt index (190° C.) was saponified with 50% aqueoussodium hydroxide in a ZSK-30 extruder having the configuration of screwelements given in Table 1 column B at a reaction temperature of about149° C. The screw speed was 500 rpm. The copolymer was fed to theextruder at a rate of 16 kg/hr., and the product was about 52%saponified. The product was visually cloudy.

This example shows that insufficient mixing was supplied by the screwconfiguration of Table 1 column B at these reaction conditions.

EXAMPLE 19

26.4 lbs./hr. of the ethylene-methyl acrylate copolymer of Example 1were fed to a Werner & Pfleiderer corrosion resistant ZSK-30 twin-screwextruder having the configuration of elements given in Table 1 column C.50% aqueous potassium hydroxide was fed into zone 3 at the rate given inTable 20. The screw speed was 500 rpm.

The extruder temperatures were substantially the same as those given inTable 19. Volatile components were removed in a two portdevolatilization section, and the second port had a vacuum of 28 in. Hg.The following table summarizes the feed rate of potassium hydroxide, themelt flow rate (230° C.), and the extent of saponification of the methylacrylate groups.

                  TABLE 20                                                        ______________________________________                                        Feed rate                                                                     (lb./hr.) of 50%                                                                            Melt flow rate of                                               aqueous potassium                                                                           ionomer of this                                                                            Extent of                                          hydroxide     Example      saponification                                     ______________________________________                                        1.87          1.66         27                                                 2.62          0.60         37                                                 3.74          0.23         53                                                 5.28          0.07         78                                                 ______________________________________                                    

COMPARATIVE EXAMPLE G

An ethylene-methyl acrylate copolymer containing 20% methyl acrylate byweight and having a melt index of 20 g/10 min. (190° C.) was fed to aWerner & Pfleiderer ZSK-40 corrosion-resistant extruder at 100 lbs/hr.4.7 lbs/hr. of 50% sodium hydroxide solution was fed to zone 3 of theextruder. The screw speed was 275 rpm.

The following extruder temperatures were measured:

                  TABLE 21                                                        ______________________________________                                        Zone No. 1      2      3     4    5     6    7                                ______________________________________                                        Temperature                                                                            200    208    279   280  278   280  281                              (°C.)                                                                  ______________________________________                                    

The vacuum on the second devolatilization zone was 27.0 in. Hg. Thereaction product was extruded, cooled in a water bath, and pelletized.The pellets were dried in a vacuum over at 65° C. and 29.5 in. Hg for 48hours. The product had a melt index of 1.6 g/10 min. (190° C.). Thehydrolysis of the product was 24%.

The polymer was made into blown film on a Victor blown film line usingthe processing conditions similar to those in Example 1. The haze of theblown film was 97%, and the 60° gloss was 43.

The SEM micrograph shown in FIG. 2 was taken on a freeze-fracturedsurface of the blown film made from this ionomer.

COMPARATIVE EXAMPLE H

An ethylene-methyl acrylate copolymer having 20 weight percent methylacrylate and a melt index of 153 g/10 min. (190° C.) was 35% hydrolyzedby the method of Comparative Example A. The melt index of this ionomerwas 9.7 g/10 min. (190° C.), and the haze of a cast film was 98%, the60° gloss was 6, and the tear strength (g/mil) in the machine directionwas 33 and in the transverse direction was 41.

EXAMPLE 20

An ethylene-methyl acrylate copolymer having 20 weight percent methylacrylate was saponified substantially by the method of Example 1. Thepercent hydrolysis and properties of the polymer are listed in thefollowing Table 22.

                                      TABLE 22                                    __________________________________________________________________________                   TENSILE          MELT ELMENDORF                                %              STRENGTH,                                                                             1° SECANT                                                                       POINT                                                                              STRENGTH,                                                                             ELONGATION                       HYDRO-                                                                              %   60°                                                                         psi     MODULUS, psi                                                                           TEMP.                                                                              g/mil   @ BREAK, %                       LYZED HAZE                                                                              GLOSS                                                                              MD  TD  MD  TD   °C.                                                                         MD  TD  MD  TD                           __________________________________________________________________________    35    13.3                                                                               55  1709                                                                              1445                                                                              7893                                                                              7667 77   12  14  350 376                          42    1.4 126  2081                                                                              1928                                                                              14831                                                                             14054                                                                              76   17  24  420 434                          50    0.5 140  2321                                                                              1984                                                                              8193                                                                              7718 73   26  22  365 405                          __________________________________________________________________________     Melt point temperature was measured using a differential scanning             calorimeter and standard methods wellknown in the art.                        Elmendorf tear strength was measured using ASTM D1922.                        Elongation at break was measured using ASTM D882.                        

The hot tack strength for these ionomers is summarized in FIG. 3.

EXAMPLE 21

Samples of ethylene methyl acrylate copolymer having the methyl acrylatecontents in following Table 23 were saponified to various degrees ofhydrolysis using substantially the method of Example 1. In addition,ethylene methyl acrylate copolymers made by the method of U.S. Ser. No.07/947,870, filed Sep. 21, 1992, where all of the methyl acrylate wasfed to a first reaction zone of a multi-zone high-pressurepolymerization reactor, were saponified to various degrees ofhydrolysis. Table 23 summarizes the melt point temperatures of theseionomers.

                                      TABLE 23                                    __________________________________________________________________________           ETHYLENE         ETHYLENE METHYL                                              METHYL ACRYLATE  ACRYLATE COPOLYMER                                           COPOLYMER MADE BY                                                                              MADE BY METHOD                                        WT. %  METHOD OF U.S. 3,350,372                                                                       OF U.S. SER. NO. 07/947,870                           METHYL %        MELT POINT                                                                            %        MELT POINT                                   ACRYLATE                                                                             HYDROLYZED                                                                             TEMP., °C.                                                                     HYDROLYZED                                                                             TEMP., °C.                            __________________________________________________________________________    12     62       90      60       97                                           12     86       83      83       99                                           12     --       --      83       98                                           12     100      87      99       93                                           20     --       --      35       92                                           20     47       87      42       91                                           20     51       86      50       91                                           20     61       83      65       92                                           20     72       64      --       --                                           24     42       64      --       --                                           __________________________________________________________________________

EXAMPLE 22

Ionomer was made substantially by the method of Example 1. This ionomerwas cast coextruded individually with three polymers on a RandcastleMini-Extruder to form three 2-layer films, where each layer was 2milthick. Adhesion strength of the 2-layer films was analyzed using TAPPIUniform Method 541, "Adhesion to Non-Porous Flexible Substrates", whichis incorporated by reference in its entirety herein. Ionomer/propylenefilm (Fina 3275) had an adhesion of 770 g/inch; ionomer/high densitypolyethylene (Chevron HiD® 9650) could not be separated; andionomer/nylon (Allied Chemical's Capron 8350) had an adhesion of 80g/inch.

The heat seal strength of the ionomer/polyethylene film above issummarized in FIG. 4.

EXAMPLE 23

Ethylene-methyl acrylate-butyl acrylate copolymer containing 10 weightpercent methyl acrylate and 10 weight percent butyl acrylate is about50% hydrolyzed substantially by the method of Example 1. This yields anethylene-methyl acrylate-butyl acrylate-sodium acrylate copolymer. It isexpected that the methyl acrylate reacts at a faster rate than the butylacrylate, so more methyl acrylate is converted to the sodium salt thanbutyl acrylate. This product is useful in applications where a highermelt-point temperature is desired, such as films or bags which contacthot food or liquids.

EXAMPLE 24

Ionomer #1, ionomer of this invention having an extent of saponificationof 50%, was formed by saponifying ethylene-methyl acrylate copolymerhaving 20 wt. % methyl acrylate with aqueous sodium hydroxide bysubstantially the method of Example 1. Ionomer #2, ionomer of thisinvention having an extent of saponification of about 83%, was formed bysaponifying ethylene-methyl acrylate copolymer having 12 wt. % methylacrylate with aqueous sodium hydroxide by substantially the method ofExample 1.

These ionomers were melt-blended in an twin-screw extruder withpolypropylene (PROFAX 6523 polypropylene) or with high-densitypolyethylene (Chevron HiD 9607, 6 melt index) in the weight ratios givenin Tables 24-26 below. Mold shrinkage was determined by forming atensile bar of ionomer in a mold and comparing the longitudinal lengthof the tensile bar to the mold length after the tensile bar sat forseveral days. Notched Izod was determined by ASTM D-256, and Vicatsoftening point was determined by ASTM D-1525.

                  TABLE 24                                                        ______________________________________                                        PROPERTIES OF POLYPROPYLENE BLENDED WITH                                      IONOMER #1                                                                    ______________________________________                                        PARTS POLYPROPYLENE                                                                            0        25    75     100                                    PARTS OF IONOMER #1                                                                            100      75    25      0                                     MOLD SHRINKAGE,  6         8    20     approx.                                mil/in.                                 24.sup.1                              VICAT SOFTENING  60       71    150    160                                    POINT, °C.                                                             NOTCHED IZOD,    7        12     2      0                                     ft-lb/in. at room                                                             temperature                                                                   ______________________________________                                         .sup.1 Value estimated from literature                                   

This data shows surprisingly little mold shrinkage and surprisinglyimproved impact resistance (as measured by notched Izod) for a blend ofionomer of this invention and polypropylene when less than about 50% ofthe blend is polypropylene.

                  TABLE 25                                                        ______________________________________                                        PROPERTIES OF POLYPROPYLENE BLENDED WITH                                      IONOMER #2                                                                    ______________________________________                                        PARTS POLYPROPYLENE                                                                            0       25      75   100                                     PARTS OF IONOMER #2                                                                            100     75      25    0                                      MOLD SHRINKAGE,  N/A.sup.2                                                                             11      18   approx.                                 mil/in.                                24.sup.3                               VICAT SOFTENING  76      150     150  160                                     POINT, °C.                                                             NOTCHED IZOD,    6        7       1    0                                      ft-lb/in. at room                                                             temperature                                                                   ______________________________________                                         .sup.2 Not available                                                          .sup.3 Value estimated from literature                                   

This data shows low mold shrinkage and good impact resistance for blendscontaining less than about 50% polypropylene, and shows surprisinglygood Vicat softening point regardless of the amount of polypropylenepresent in the blend.

                  TABLE 26                                                        ______________________________________                                        PROPERTIES OF HIGH DENSITY POLYETHYLENE                                       BLENDED WITH IONOMER #1                                                       ______________________________________                                        PARTS POLYETHYLENE                                                                              0       25     75   100                                     PARTS OF IONOMER #1                                                                             100     75     25    0                                      MOLD SHRINKAGE,   6        4     22   approx.                                 mil/in.                                24.sup.4                               VICAT SOFTENING   60      82     113  160                                     POINT, °C.                                                             NOTCHED IZOD,     7       10      5    0                                      ft-lb/in. at room                                                             temperature                                                                   ______________________________________                                         .sup.4 Value estimated from literature                                   

This data shows surprisingly low mold shrinkage when less than about 50%high-density polyethylene is blended with ionomer of this invention, andalso shows surprisingly good impact resistance for blends ofhigh-density polyethylene and ionomer.

EXAMPLE 25 Ethylene-alkylacrylate Copolymer Blended with Ionomer

Ethylene-methyl acrylate copolymer having 16 wt. % methyl acrylate wasmade by the method of U.S. Ser. No. 947,870 by feeding all of the methylacrylate to a first reaction zone. Ionomer of this invention was made bysaponifying this copolymer with aqueous sodium hydroxide bysubstantially the method of Example 1, so that the resultant copolymerhad an extent of saponification of about 63%. A blend of 10 parts ofethylene-methyl acrylate copolymer having 20 wt. % methyl acrylate and 2melt index and 90 parts of the ionomer was made by the method of Example24. Properties listed in Table 27 were observed:

                  TABLE 27                                                        ______________________________________                                                                    ETHYLENE-                                                 IONOMER  BLEND OF   METHYL                                                    OF THIS  THIS       ACRYLATE                                                  EXAMPLE  EXAMPLE    COPOLYMER                                         ______________________________________                                        HAZE, %   0.5        0.6        15                                            60° GLOSS                                                                        151        150        70                                            HOT TACK:.sup.5                                                               80° C.                                                                           0.13       0.5        1.4.sup.6                                     85° C.                                                                           0.13       1.1        --                                            90° C.                                                                           0.18       2.2        --                                            95° C.                                                                           1.7        2.1        --                                            100° C.                                                                          1.9        2.3        --                                            105° C.                                                                          2.0        2.4        --                                            110° C.                                                                          2.0        2.1                                                      115° C.                                                                          2.5        2.3        --                                            120° C.                                                                          2.6        2.4        --                                            125° C.                                                                          2.2        2.2        --                                            ______________________________________                                         .sup.5 Newtons/inch                                                           .sup.6 Sample burned through                                             

Also, ethylene methyl acrylate ionomer was made by saponifying ethylenemethyl acrylate copolymer having 20 wt. % methyl acrylate and 400 meltindex using 50% aqueous NaOH to achieve 50% saponification; this ionomercontained 5% by weight of a low molecular weight ethylene-acrylic acidcopolymer, available from Allied Signal as "AC Copolymer" to improve theprocessability of the ionomer. 5 parts by weight of this ionomer werefed simultaneously with 95 parts of ethylene-methyl acrylate copolymerhaving 20 wt. % methyl acrylate and a melt index of 2.4 to a preheatedscrew and extruded into strands. The strands were air-cooled on a 10foot conveyor belt and pelletized in a Conair pelletizer. The pelletswere dried in a vacuum oven at 27 in. Hg and at 67° C. for several days.The pelletized blend had a melt index of 1.4 g/10 min.

A cast film was made using a Randcastle Miniextruder. The film wasvisually clear and mechanically strong. Also, the heat-seal strengthappeared to be very good. Two layers which had been heat-sealed togethercould not be pulled apart by hand easily.

This data shows good haze, gloss, heat seal and hot tack for a blend ofethylene-alkyl acrylate copolymer and ionomer of this invention.

EXAMPLE 26 Reactive Blending of Polyamide with Ionomer

20 parts by weight of ionomer of Example 1 is melt-blended in atwin-screw reactive extruder with 80 parts by weight of nylon 6. 2.6parts by weight of acetic acid is added directly to a first reactionzone of the twin-screw reactive extruder to react the ionomer withterminal amine and/or carboxyl groups on the nylon. The reacted blend isdevolatilized in a devolatilization section of the reactive extruder.The resultant polymer is expected to have better room and lowtemperature impact resistance and better scratch resistance.

Optionally, melted reacted blend, before or after devolatilization, iscontacted in a second reaction zone with an amount of 50% aqueous NaOHthat is sufficient to neutralize at least a portion of the acidity onthe ionomer portion of the reacted polymer. This mixture isdevolatilized in a devolatilization zone of a reactive extruder.

EXAMPLE 27 Reactive Blending of Ethylene-methyl Acrylate Copolymer WithIonomer

80 parts by weight of ionomer of Example 1 is melt-blended in atwin-screw reactive extruder with 20 parts by weight of ethylene-methylacrylate copolymer having 20 wt. % methyl acrylate and a melt index of2. 0.02 part by weight tetraethyl titanate is added directly to a firstreaction zone of the twin-screw reactive extruder to transesterify theionomer and the ethylene-methyl acrylate copolymer. The reacted blend isdevolatilized in a devolatilization section of the reactive extruder.The resultant polymer is expected to have improved tear resistance andreduced stiffness.

EXAMPLE 28 Reactive Blending of Ethylene-methyl Acrylate Copolymer WithIonomer

20 parts by weight of ionomer of Example 1 is melt-blended in atwin-screw reactive extruder with 80 parts by weight of ethylene-methylacrylate copolymer having 20 wt. % methyl acrylate and a melt index of2. 0.02 part by weight tetraethyl titanate is added directly to a firstreaction zone of the twin-screw reactive extruder to transesterify theionomer and the ethylene-methyl acrylate copolymer. The reacted blend isdevolatilized in a devolatilization section of the reactive extruder.The resultant polymer is expected to have increased scratch resistance,greater stiffness, and improved tensile properties.

We claim:
 1. A blow-molded article comprising a copolymer ofalpha-olefins having from two to eight carbon atoms, esters of alpha,beta-ethylenically-unsaturated carboxylic acids having from four totwenty-two carbon atoms, and metal salts of acrylic or methacrylic acid,wherein the copolymer has a haze of no more than ten percent as measuredby ASTM method D
 1003. 2. The article of claim 1 wherein the copolymercontains esters in an amount in the range of from about 2.3 mole percentto about 7.4 mole percent based on the copolymer.
 3. The article ofclaim 1 wherein the metal salt of acrylic or methacrylic acid comprisesbetween about 1.9 and about 7.5 mole percent of the copolymer.
 4. Aneasy-open package comprising a copolymer of alpha-olefins having fromtwo to eight carbon atoms, esters of alpha,beta-ethylenically-unsaturated carboxylic acids having from four totwenty-two carbon atoms, and metal salts of acrylic or methacrylic acid,wherein the copolymer has a haze of no more than ten percent as measuredby ASTM method D
 1003. 5. The package of claim 4 wherein the copolymercontains esters in an amount in the range of from about 2.3 mole percentto about 7.4 mole percent based on the copolymer.
 6. The package ofclaim 4 wherein the metal salt of acrylic or methacrylic acid comprisesbetween about 1.9 and about 7.5 mole percent of the copolymer.